Aluminum alloy composite and method for joining thereof

ABSTRACT

The object of the present invention is to strongly join an aluminum alloy part with an FRP prepreg. An object obtained by subjecting an aluminum alloy to a suitable liquid treatment so as to form a surface having large, micron-order irregularities and also fine irregularities with a period of several tens of nanometers, eliminating the presence of sodium ions from the surface and additionally forming a surface film of aluminum oxide, which is thicker than a natural oxide layer, has been found to have a powerful adhesive strength with epoxy-based adhesives. By simultaneously curing an FRP prepreg which uses the same epoxy-based adhesive in the matrix, an integral composite or structure in which FRP and aluminum alloy have been united at a joining strength of unprecedented magnitude is produced.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 12/530,940 filedon Sep. 11, 2009, which is a national stage of international applicationno. PCT/JP2008/054539 filed on Mar. 12, 2008, which claims foreignpriority of Japanese Patent Application 2007-062376 filed on Mar. 12,2007 in Japan.

FIELD OF THE INVENTION

The present invention relates to methods for joining metals with metalsor metals with plastics that are used in transportation machinery,electrical equipments, medical instruments, general machinery, otherindustrial machinery, consumer equipments or the like; to compositesthereof; and to methods for manufacturing the same. More specifically,the present invention relates to aluminum alloy composites and joiningmethods for integrally joining optimal aluminum alloy parts and plasticparts together, suitable for use as transportation machinery componentsthat are required to be lightweight, such as automotive parts andaircraft parts.

BACKGROUND OF THE INVENTION

With the recent rise of energy prices, further technical innovations arebeing sought in aircraft. That is, in the new model aircraft and the newmodel concepts recently announced by the Boeing Company (U.S.) andAirbus (France), the utilization of aluminum alloys such as extra superduralumin (designated as “A7075” according to the Japanese IndustrialStandards (JIS)) and extra duralumin (similarly designated as “A2024”)for reducing the weight of the fuselage has been abruptly decreased andthe utilization of carbon fiber reinforced plastic (abbreviated below as“CFRP”) is being increased by a corresponding amount.

A7075 (extra super duralumin), which is one type of aluminum alloy, hasa specific gravity of about 2.7, whereas CFRP has a specific gravity of1.6 to 1.7, making it incomparably lighter. Up until now, theutilization of CFRP as a material for aircraft has been increased inmilitary applications such as fighter planes and combat helicopters,while use as a civilian aircraft material has not grown so much asanticipated due to the need to develop know-how on manufacturing largecomponents and because of obstacles from the standpoint of cost. The useof CFRP has been avoided in civilian applications, in spite of theirlight weight, high strength and high corrosion resistance. Lately,however, in addition to research and development by the above twoleading civilian aircraft manufacturers, the rise of the price of crudeoil and its duration have made it imperative to examine ways of reducingthe airframe weight.

The automotive industry as well, in order to cope with the rise of crudeoil prices and environmental issues, is promoting the development ofhybrid vehicles, electric cars and, in Europe, high-performance dieselengine vehicles. Moreover, it is expected that fuel cell vehicles, whichhave the highest energy conversion efficiency, will someday seewidespread use. Although significant advances have been made in thedevelopment of fuel cells, the largest and most difficult problem thatremains for use in automobiles is how to safely and smoothly handlehydrogen fuel, for which laborious work has been made. While safety ismost important in civilian use, the obstacles are too large to make it aroutine matter for general users to deal with cars loaded with hydrogengas under several hundred atmospheres of pressure. Hence, the currentliquid fuel system is not likely to change for the time being. In thissense, reducing the weight of vehicle construction is important forachieving real improvements in the power system. In fact, aluminum alloymaterials are being applied increasingly in some types of vehicles andit is predicted that use of CFRP will be required someday.

In aircraft manufacture, the increased utilization of CFRP materialsentails an increase in material expenses due to the high-cost CFRPmaterials, in addition to which it presents technical problems. One suchproblems is that, even in the latest Airbus and Boeing aircraft forwhich mass production has already been decided, it is estimated that theutilization of aluminum alloys will top 50% in terms of weight, withboth CFRP materials and A7075 materials being used. CFRP materials willbe used in areas close to the wing tips and A7075 materials will beused, as in the past, in central structure areas of the fuselage.Joining of the two materials will generally be done with rivets or withbolts and nuts, while special products will be required for thispurpose.

This is because of the large differences between CFRP materials andmetals in their basic properties. Metal materials have a largeelongation (elongation at break), that of A7075 being 10 to 16%, whereasCFRP has an elongation of only several percent. When a strong tensileforce is applied to these materials, the metal material undergoeselastic stretch (in accordance with Young's modulus, elongation andcontraction that is proportional to the force) up to a certain strength;when a force that exceeds this limit is applied, elongation in excess ofYoung's modulus takes place, where break occurs at 110 to 116% of theoriginal length (100%) for A7075. On the other hand, for CFRP, whenpulled in a direction parallel to the fibers, elongation of the carbonfibers themselves is only 1 to 2%. When a large tensile load is appliedthat exceeds the range of elongation and contraction in accordance withYoung's modulus, the carbon fibers break and the CFRP tears. In otherwords, CFRP has a small range in the ability of the material to absorbforces by undergoing elongation itself.

The same is true not only for tensile forces but also for crushingforces (compressive forces). That is, when tightened with bolts andnuts, even if the compressive forces exceed a certain limit, a metalwill be deformed itself, enabling break to be avoided. However, when acompressive load is applied to CFRP, the force is first supported by thecured epoxy resin; with the application of an excessive pressing force,the epoxy resin is forced to spread peripherally and be deformed butspreading is limited by the carbon fibers, as a result of which theresin does not move and thus cannot be deformed, leading ultimately tofailure.

In short, when a throughhole is formed in CFRP, a bolt is inserted intothe hole and a nut threaded on the bolt is used to tighten the CFRP withan excessive torque, the CFRP undergoes compressive break. Because thelarge differences between the physical properties of both materials aredue to inherent differences between a metal part, which is composed ofmetallic bonds between atoms, and epoxy resins and carbon fibers, whichare composed of covalent bonds between carbon atoms and the like, thereare basically no means for improving the properties themselves.Therefore, when both are tightened and secured with bolts and nuts, theonly solution is to avoid applying excess pressure so as to preventbreak on the CFRP side. This requires the development and use of specialbolts and nuts. It has even been reported that the success by a certaincorporation in developing such a bolt structure helped to spur thecompetition today in development of civilian aircrafts.

In future aircrafts, regardless of the degree to which the utilizationof CFRP increases, the utilization of light metal materials will nevergo to zero, which means that techniques for easily joining CFRPmaterials with aluminum alloy materials will continue to be veryimportant basic technology. There is another problem as to releasing ofthe CFRP prepreg from the metallic mold after its heat-curing. Theprepreg undergoes heat-curing in a pressurized state under compressiveforces applied by the metallic mold. In this operation, because theepoxy resin functions as an adhesive with respect to the mold as well,it is necessary to apply a release agent between the mold and theprepreg. As a result, infiltration of the release agent (generally asilicone oil-type release agent) into the CFRP product is unavoidable,which makes it impossible to achieve the highest physical propertiesinherent to the epoxy resin. Even minor decreases in quality are issuesthat must be resolved for use in structures for high-speed movingmachinery such as aircrafts and automobiles. The present invention wasconceived in order to provide a solution to such problems.

The inventors have made inventions as to techniques for securely joininga plastic part formed by injection molding with a metal part that hasbeen inserted beforehand into the metallic mold for injection,specifically, aluminum alloy parts, magnesium alloy parts, copper alloyparts, titanium alloy parts, stainless steel parts, etc. (whichtechniques are referred to below as “injection joining” techniques) (seePatent Document 1: WO 03/064150 A1, Patent Document 2: WO 2004/041532A1, Patent Document 4: Japanese Patent Application No. 2006-329410,Patent Document 5: Japanese Patent Application No. 2006-281961, PatentDocument 6: Japanese Patent Application No. 2006-345273) and PatentDocument 6: Japanese Patent Application No. 2006-354636).

A major factor was the discovery of surface treatment methods carriedout beforehand on the metal to be inserted. The inventors anticipatedthat the surface shape of the metal obtained by such surface treatmentwould have a desirable effect not only on injection joining but also onjoining (adhesion) with ordinary adhesives.

In the above-described inventions as to “injection joining”, the surfacestate desired in the metal alloy to be used can be summarized in termsof the following conditions (1) to (3). The first of these conditions(1) is that the rough surface obtained by chemical etching haveirregularities (depressions and protrusions) with a period of 1 to 10μm, with the height difference between the depressions and protrusionsbeing about one-half of the period, i.e., 0.5 to 5 μm. The reason forthis is that, when the molten resin flows into the metallic mold havinga temperature well over a hundred and several decade degrees Centigradelower than the melting point of the resin under a high pressure ofseveral hundred to a thousand atmospheres, the diameter of thedepressions into which the resin can somehow manage to penetrate as itcrystallizes and hardens is 1 to 10 μm.

However, it is actually difficult that cover 100% of an aluminum alloysurface in this way with such a rough surface, given the variability ofchemical reactions. It is practically regarded that such a surfaceroughness satisfies the above-mentioned roughness conditions, for whicha curve indicating depressions and protrusions with an irregular periodranging from 0.2 to 20 μm and having a maximum height difference in arange of 0.2 to 10 μm as measured with a surface roughness tester can betraced, or for which a mean peak spacing (RSm) is 0.8 to 10 μm and amaximum height (Rz) is 0.2 to 10 μm analyzed with a scanning probemicroscope, where such amounts as RSm and Rz are defined in the JISstandard (JIS B 0601:2001). The inventors, having recognized andconcluded that the period of the depressions and protrusions on an idealrough surface is, as noted above, 1 to 10 μm, refer in the presentinvention to a rough surface with a surface roughness defined in thisway as a “surface with micron-order roughness,” which is a readilyunderstood technical term.

The second condition (2) is that, when the rough surface is viewed witha magnification of an electron microscopic level, it has a finelyirregular surface of depressions and protrusions with a period of 10 to500 nm, most preferably a finely irregular surface with a period of 40to 50 nm. The third condition (3) is that the surface is covered with athin layer of metal oxide which is either thicker or stronger than anordinary natural oxide layer for that particular metal alloy. Each ofthese three conditions required on the metal alloy side were attained,as noted above, for all of the following: magnesium alloys, titaniumalloys, copper alloys, stainless steel alloys, aluminum alloys, etc., asa result of which it was possible to achieve a high shear breakingstrength between the metal and the cured resin of at least 20 to 30 MPawith injection joining. This clearly proved the correctness of thehypothesis that the above three conditions are essential for injectionjoining. At this point, the inventors expected that this hypothesisshould obviously have desirable effects also in joining (adhesion) withadhesives.

Hence, the inventors proposed the following hypothesis concerningadhesive joining. First, the metal alloy piece with a surface whichsatisfies the three above mentioned conditions is prepared in the sameway as that used in the above described injection joining experiment anda liquid, one-pack epoxy adhesive is applied to the metal piece. Next,the metal piece is subjected to such steps as being placed in a vacuumstate and then returned to standard pressure, causing the adhesive toinfiltrate and smoothly coat the finely textured face of the metal alloysurface. The adhesive is then cured through heating. It was thoughtthat, in this way, the liquid epoxy adhesive would be able to enter intothe depressions of the micron-order roughness of condition (1) for themetal alloy surface at an inflow pressure of only about one atmosphere.If such penetration is possible, the epoxy adhesive will be cured withinthese valleys with subsequent heating.

In this case, the inner walls of these depressions have thenanometer-level finely irregular surface of condition (2). Completepenetration of the epoxy adhesive to the depths of the fine depressionsformed in the finely irregular surface of (2) is presumed to bedifficult. However, some of the epoxy adhesive does extend inside theopenings of the fine depressions and is cured. In such a case, the epoxyadhesive that has been cured inside a large depression achieves thestate of being secured (engaged) at the interior of the depression byinnumerable spikes, which should make it difficult to be peeled awayfrom the metal substrate by an external force. When the cured epoxyresin is forcibly peeled away, because the metal oxide layer ofabove-described condition (3) for the surface in contact with the spikeshas a sufficient thickness to exhibit the hardness of this ceramicmaterial, deformation on the metal alloy side is limited, making itimpossible to pull out the epoxy resin within the large depression.Ultimately, the epoxy resin itself breaks near the opening of the largedepression. In such cases, the force required for break far exceeds theadhesive strength data for hitherto known adhesives.

The correctness of this hypothesis has, in fact, already been proven,first for aluminum alloys, then for magnesium alloys, copper alloys,titanium alloys and stainless steel alloys. Subsequent to the presentinvention, the inventors are occupied in verification tests and plan topropose a group of inventions concerning various metal alloys. Based onthese tests, the inventors believe that the above hypothesis concerningadhesive joining is correct, while it will accept the approval orcriticism from many scientists and chemists. In the present invention,the inventors refer to this hypothesis as “NAT (Nano AdhesionTechnology)”. With NAT, as explained above in regards to adhesion withan adhesive, joining can be understood as an entirely physical effect,that is, as an anchoring effect. Without such an understanding, it isimpossible to explain the immense joining strengths of 500 to 700kgf/cm² (50 to 70 N/mm²=50 to 70 MPa), measured as the shear strength atbreak and the tensile strength at break, which are exhibited with theuse of an epoxy-based adhesive, not only for aluminum alloys but alsofor other metal alloys as well.

In addition, it has been mentioned above as condition (1) that largedepressions and protrusions, that is, depressions and protrusions with aperiod of 1 to 10 μm, are desirable, while this NAT applies not only tothe aluminum alloys shown in the present invention but it has beendemonstrated also, for example, for copper alloys, titanium alloys,stainless steel alloys and common steel materials. In cases wheredepressions and protrusions larger than described above are present and,conversely, in cases where depressions and protrusions that are too muchsmaller than described above are present, the joining strength due tojoining with an adhesive became lower. For depressions that are toolarge, the most likely reason is such that the density of depressionsthat forms per unit surface area becomes low, thus reducing theanchoring effect. For depressions that are too small, penetration of theepoxy adhesive into the interior is probably insufficient.

By utilizing the above-described joining strength according to NAT, itis possible to achieve the many needs mentioned in the precedingsection. First, in the case of adhesive joining between metal alloys forwhich surface treatment according to NAT hypothesis was made, a verystrong adhesive force can be obtained between metal alloys by using anepoxy adhesive. This is the case both in joining between aluminum alloysand in joining between an aluminum alloy and a titanium alloy. Thereason is that the joining strength itself does not arise between themetals but it rather arises between the respective metals and the epoxyresin. Also, a fiber-reinforced plastic (FRP) material in which theepoxy resin is used as the matrix is, not surprisingly, the mosttrouble-free mating material for adhesive joining with a metal alloypiece. It can be appreciated that, by pressing together a FRP prepregand an aluminum alloy part that has been coated with an epoxy adhesive,raising the temperature and simultaneously curing the epoxy resins onboth sides, joining (anchoring) will be easier than between metals.

One conceivable form of this adhesion is a structure in which the FRPmaterial is sandwiched between thin sheets of aluminum alloy, that is, alaminated structure. Although there is an increase in weight,degradation of the epoxy resin by a release agent can be prevented,because a mold release agent for the prepreg is not necessary. Also, incases where a sandwich structure is formed in which part of the prepregrather than the entire surface is placed between thick sheets ofaluminum alloy to form a sandwich structure, throughholes are formed inthe structure, bolts are passed through the holes and joining to anotherpart is carried out, break of the CFRP portion can be avoided even whenthe bolts are over-tightened.

Additionally, in a plate-like or tubular structural member formedintegrally of an aluminum alloy member at the ends and a CFRP member asthe main material at the center, connection with bolts and nuts, fittingor some other known metal joining method may be employed by utilizingthe ends thereof, facilitating assembly and disassembly, thus giving amember compatible with large-volume production. This should be helpfulin reducing weight and increasing strength not only in aircrafts butalso in vehicles such as automobiles, in mobile electronic andelectrical equipments, in robot machineries or the like. Today, CFRPmaterials are very familiar materials. The ability to employ suchmaterials in vehicle applications will enable major contributions to bemade to the energy-saving and environmentally responsible society in thefuture.

SUMMARY OF THE INVENTION

The present invention, which was conceived in order to solve theproblems described above, achieves the following objects.

One object of the present invention is to joining an aluminum alloycomposite obtained by joining a CFRP material with an aluminum alloy anda method for manufacturing such a composite.

A further object of the present invention is to provide an aluminumalloy composite and a method for manufacturing the same, which enable aCFRP material and an aluminum alloy part to be joined without using afastening means such as a bolt and nut having a special construction,that is, which enables such joining to be carried out with ordinaryfastening means.

A still further object of the invention is to provide an aluminum alloycomposite and a method for manufacturing the same, which do not requirea release agent when a CFRP material and an aluminum alloy are joined(anchored).

The invention employs the following means to achieve the above objects.

The aluminum alloy composite of the present invention is composedessentially of a first metal part made of a first aluminum alloy havinga micron-order surface roughness formed by chemical etching on a surfacethereof, the surface having thereon a thin layer of aluminum oxide witha thickness of at least 2 nm that is free of sodium ions and the surfaceroughness having formed therein an ultra-fine irregular surface formedof depressions or projections having 10 to 100 nm diameter andsubstantially equal depth or height; and

an adherent part joined to the first metal part with an epoxy-basedadhesive that has penetrated into the ultrafine irregular surface.

The method for manufacturing an aluminum alloy composite of the presentinvention is composed essentially of a step of shaping an aluminum alloypart by mechanical working from a casting or an intermediate material; achemical etching step by immersing said shaped aluminum alloy part in astrongly basic aqueous solution; a neutralizing step by immersing saidaluminum alloy part in an aqueous solution of an acid after the chemicaletching step; an ultrafine etching step by immersing the aluminum alloypart in an aqueous solution containing at least one selected from amonghydrazine hydrate, ammonia and water-soluble amine compounds so as toform on the part an ultrafine irregular surface after the neutralizingstep; a step of coating said ultrafine irregular surface of the aluminumalloy part with an epoxy adhesive; a step of forming a fiber-reinforcedplastic prepreg material containing epoxy resin component into arequired shape; a step of attaching the shaped prepreg material to theepoxy adhesive-coated surface of the aluminum alloy part; and a step ofpositioning said prepreg material and the aluminum alloy part and curingthe epoxy-based adhesive and the epoxy resin component through applyingheat and pressure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view showing a firing jig for curing an aluminumalloy piece and a CFRP prepreg within a hot-air dryer and a method ofsetting up the same.

FIG. 2 shows a composite, which is also a test specimen for measuringthe joining strength therebetween by applying a tensile load to break,obtained by joining an aluminum alloy sheet and a CFRP prepreg with anepoxy-based adhesive.

FIG. 3 is a schematic view showing an exemplified construction obtainedby using bolts and nuts to join an aluminum alloy piece-FRP prepregcomposite with another metal structural member.

FIG. 4 shows a test specimen obtained by joining together two pieces ofaluminum alloy with an epoxy adhesive, the purpose of the specimen beingto measure the joining strength between the aluminum alloy pieces byapplying a tensile load to break.

FIG. 5 is an electron micrograph of a piece of A7075 aluminum alloy thatwas etched with an aqueous solution of caustic soda.

FIG. 6 is an electron micrograph of a piece of A7075 aluminum alloy thatwas etched in an aqueous solution of caustic soda and then neutralizedin an aqueous solution of nitric acid.

FIG. 7 is an electron micrograph of a piece of A7075 aluminum alloy thatwas etched with an aqueous solution of caustic soda, neutralized with anaqueous solution of nitric acid and then etched in an aqueous solutionof hydrazine hydrate as an ultrafine etching.

FIG. 8 is an electron micrograph of a piece of A7075 aluminum alloy thatwas etched with an aqueous solution of caustic soda, neutralized with anaqueous solution of nitric acid, then etched in an aqueous solution ofhydrazine hydrate as an ultrafine etching and subsequently treated withaqueous hydrogen peroxide.

FIG. 9 is an electron micrograph of a piece of A5052 aluminum alloy thatwas etched with an aqueous solution of caustic soda, neutralized with anaqueous solution of nitric acid and then subjected to ultrafine etchingtreatment for 1 minute in an aqueous solution of hydrazine hydratehaving a concentration of 3.5%.

FIG. 10 is an electron micrograph of a piece of A5052 aluminum alloythat was etched with an aqueous solution of caustic soda, neutralizedwith an aqueous solution of nitric acid and then subjected to ultrafineetching treatment for 2 minutes in an aqueous solution of hydrazinehydrate having a concentration of 3.5%.

FIG. 11 is an electron micrograph of a piece of A5052 aluminum alloythat was etched with an aqueous solution of caustic soda, neutralizedwith an aqueous solution of nitric acid and then subjected to ultrafineetching treatment for 4 minutes in an aqueous solution of hydrazinehydrate having a concentration of 3.5%.

FIG. 12 is an electron micrograph of a piece of A5052 aluminum alloythat was etched with an aqueous solution of caustic soda, neutralizedwith an aqueous solution of nitric acid and then subjected to ultrafineetching treatment for 8 minutes in an aqueous solution of hydrazinehydrate having a concentration of 3.5%.

FIG. 13 is a graph of the results presented in Table 1.

FIG. 14 is a graph of the results presented in Table 2.

FIG. 15 shows the results by observation of the A5052 aluminum alloyobtained in Experiment example 1 with a scanning probe microscope.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The constituent features of these inventions will be describedrespectively below in detail.

[Aluminum Alloy Part]

The aluminum alloy used in the present invention may be of any type, solong as it is an aluminum alloy. For example, all malleable aluminumalloys, such as those defined in Japanese Industrial Standard (JIS)A1000 series to 7000 series (e.g., corrosion-resistant aluminum alloys,high-strength aluminum alloys, heat-resistant aluminum alloys, etc.) andaluminum alloys for casting, such as JIS ADC 1 to 12 (aluminum alloysfor die casting), may be used. In the case of casting alloys, shapedforms that may be used include parts that have been shaped by dyecasting or such parts that have additionally been shaped by mechanicalworking. In the case of malleable alloys, a plate stock or the like asan intermediate material and a part, which has been shaped from the sameby mechanical working such as hot pressing, may be used.

[Surface Treatment, Pre-Treatment of Aluminum Alloy Parts: Theories andBasic Thought Thereof]

It is preferable to immerse the aluminum alloy part at first in adegreasing tank and remove any fats, oils and oil-based agents that haveadhered to the part in mechanical working. A special degreasingtreatment is not required in the present invention. Rather, it isdesirable to prepare a warm aqueous solution by adding a commerciallyavailable degreasing agent for aluminum alloys to hot water in theconcentration specified by the chemical manufacturer and rinse thealuminum alloy part by immersing it in the solution. That is, degreasingtreatment by a method commonly used on aluminum alloys will suffice.Although there will be some variation depending on the particulardegreaser product, with an ordinary commercially available product,immersion is carried out for a period of 5 to 10 minutes at aconcentration of 5 to 10% and at a solution temperature of 50 to 80° C.

In subsequent pretreatment steps, the treatment method will differaccording to whether the aluminum alloy includes a relatively largeamount of silicon or has only a low level of such ingredients. In thecase of alloys having a low silicon content, i.e., malleable aluminumalloys such as A1050, A1100, A2014, A2024, A3003, A5052 and A7075, atreatment method like the following is preferred. That is, it isdesirable for promoting good reproducibility of the subsequent alkalietching step to immerse the aluminum alloy part in an acidic aqueoussolution for a short time and then to rinse with water, thus allowingthe acid ingredient to be adsorbed onto the surface layer of thealuminum alloy part. This treatment, which could be referred to as apreliminary pickling step, may be carried out using a dilute aqueoussolution of an inexpensive mineral acid such as nitric acid,hydrochloric acid or sulfuric acid at a concentration of one to severalpercent. Next, etching is carried out by immersing the aluminum alloypart in a strongly basic aqueous solution and rinsing with water.

Such etching strips away fats, oils and scum remaining on the surface ofthe aluminum alloy along with the surface layer of the aluminum alloy.Simultaneously with such stripping, the surface comes to have amicron-level roughness, i.e., a mean peak spacing (RSm) of 0.8 to 10 μmand a maximum height (Rz) of 0.2 to 5.0 μm in terms of the JIS standards(JIS B 0601: 2001; ISO 4287: 1997; ISO 1302: 2002). When examined with ascanning probe microscope of the type in use today, these numericalvalues are automatically calculated and output of them is given.However, there are cases where, when numerical values are displayed forthe fine surface irregularities by automated output, the calculated RSmvalues do not represent the actual state. For better results, it isnecessary to visually reconfirm the RSm values on a roughness curvegraph that can be generated as output by the scanning probe microscopeand represent this irregular surface state.

If, on visual inspection of the roughness curve graph, the roughnessstate is one where the height difference falls in a range of 0.2 to 5 μmat irregular periods within a range of 0.2 to 20 μm, the actual state issubstantially the same as that mentioned above. Such visual inspectionmethod is advantageous because, in cases where automatic calculationsare judged to be unreliable, a determination can easily be made byvisual inspection. To summarize, using the technical term definedherein, the surface of the aluminum alloy part is formed to be “asurface with micron-order roughness.” The solution used is preferably anaqueous solution of caustic soda at a concentration of one to severalpercent, with immersion being carried out for several minutes atpreferably 30 to 40° C. Next, it is preferable to complete pretreatmentby again immersing the aluminum alloy part in an acidic aqueoussolution, then rinsing with water to remove sodium ions. The inventorsrefer to this as the neutralization step. It is especially preferablefor this acidic aqueous solution to be an aqueous solution of nitricacid having a concentration of several percent.

In the case of aluminum alloys for casting, such as ADC 10 and ADC 12,it is preferable for the procedure to include the following steps. Thatis, following the degreasing step in which oils and fats are removedfrom the surface of the aluminum alloy, it is desirable to carry outpreliminary pickling and etching in the same way as in theabove-described step. As a result of such etching, copper components orsilicon components which do not dissolve under strongly basic conditionsbecome fine-grained black smut (because such contaminants are referredto in the plating industry as smut, this usage is followed here aswell). It is thus desirable to dissolve and strip away this smut, thenimmerse the aluminum alloy part in an aqueous solution of nitric acidhaving a concentration of several percent. With immersion in an aqueoussolution of nitric acid, the copper smut is dissolved and the siliconsmut rises off the aluminum alloy surface.

In the case where the alloy used is one having a large amount of siliconcomponents, such as ADC 12, if the alloy is only immersed in an aqueoussolution of nitric acid, silicon smut will continue to adhere to thesurface of the aluminum alloy substrate and will not be completelystripped away. Therefore, it is preferable to carry out ultrasoniccleaning in which the part is immersed in a water tank and ultrasonicvibration is given to the water, thereby physically stripping off thesilicon smut. While this does not remove all the smut, it is sufficientfor practical purposes. Pretreatment may be brought to an end at thispoint, although it is preferable to once again immerse the part in adilute aqueous solution of nitric acid for a short time and rinse itwith water. This completes pretreatment. Because pretreatment ends withimmersion in an acidic aqueous solution and rinsing with water, nosodium ions remain. The sodium ions are explained below.

Based on experimental findings, the joining strength which is given whentwo pieces of aluminum alloy are joined with each other using an epoxyadhesive is determined substantially by the micron-order roughness andthe nanometer-order, ultrafine irregular shape characteristics of thesurfaces with depressions and protrusions. The experimental findingsshow that, by searching for the immersion conditions, etc. when etchingis carried out with an aqueous solution of caustic soda, if suchconditions mentioned above that the NAT hypothesis are satisfied inrespect of surface configuration, even if it be occasional, asurprisingly strong adhesive strength can be obtained. However, oncesurface treatment has been finished in case of treatment that involvesonly etching with caustic soda, sodium ions will remain in the aluminumalloy surface layer even with more than adequate water rinsingthereafter. Because sodium ions have a small particle size, they migrateeasily. Even after painting or joining has been carried out, in a wetstate of the overall assembly, sodium ions which have remained presentare entrained by water molecules passing through the resin layer and arecollected at the metal/resin interfacial surface for some reason, wherethey promote oxidation of the aluminum surface.

That is, corrosion of the aluminum alloy surface occurs, as a result ofwhich separation between the substrate and the paint film or adhesive ispromoted. Given such circumstances, there is as yet no reason to carryout etching in an aqueous caustic soda solution as an aluminum alloypretreatment prior to joining. Accordingly, even today, the standardpretreatment method for strong adhesive joining is regarded to bechromate treatment, in which the aluminum alloy is immersed in anaqueous hexavalent chromium compound solution of potassium bichromateand chromium trioxide, or anodization and use in an unsealed state. Inshort, prior to pay attention to enhancing the adhesive strength byetching, primary aim was taken at prevention of corrosion anddegradation of the aluminum alloy surface.

However, the etching of aluminum alloys with caustic sodium has not beenabandoned altogether and is still commonly used in pretreatment forpainting. Generally, an extreme adhesive strength is not required inpainting, for it is thought that, other than in outdoor use applicationswhere the product is placed in the weather, immersion in water will notoccur. Moreover, unless the product is of a type where, for example, thepaint film is to be guaranteed for ten years, such painting pretreatmentis not unreasonable. Without being based on such easy-going reasoning,the main subject of the present invention is to achieve a long-termjoining stability. To this end, the most important issue is to get ridof sodium ions.

Sodium in Aluminum Alloy

The sodium (Na) present in the aluminum alloy will be also discussed. Inthe aluminum metal manufacturing process, bauxite is dissolved in anaqueous solution of caustic soda to give a high-purity aluminumcompound, which is then electrolytically reduced to yield aluminummetal. In this manufacturing process, the presence of sodium as animpurity in the aluminum metal is unavoidable. However, in currentmetallurgical technology, it is possible to suppress the sodium contentin aluminum alloys to an extreme degree. Therefore, in an ordinaryenvironment in which there is no acid-base mist, corrosion does notadvance in commercially available aluminum alloys today when directwetting (liquid water) is not present. Corrosion actually proceeds at ahigh rate when there is wetting, salt (sodium chloride) from sea windsand heating with sunlight. That is, when commercially available aluminumalloys are used outdoors in coarse environments, such as in towns andcities located near the seashore where sea winds are strong and theatmospheric temperature is high, the rate of corrosion is high.

The solution to avoid such corrosion is generally to coat the entiresurface with paint, adhesive or the like. When this is done, it isessential that cracks or fissures are not formed in the paint film oradhesive layer and further it is important to keep salt-containing waterfrom entering such cracks and fissures and penetrating to the surface ofthe aluminum alloy. When such measures are taken, it is not alwaysnecessary for surface treatment of the aluminum alloy to entail commonchromate treatment. As long as the paint film has a good weatherresistance and adhesion between the paint film and the substrate isgood, even in an adverse environment, the aluminum alloy will be durablelong enough with painting alone. In particular, with the use ofhexavalent chromium currently being in the course of worldwiderejection, chromate treatment can no longer be regarded as a desirablemethod for surface treatment of aluminum alloys. Today, many paints withexcellent durability and adhesives having outstanding moisture and heatresistance are commercially available. In light of the above, theinventors have attempted to optimize the conditions to be sought on thealuminum alloy side, in order to maintain a strong joining between paintor adhesive and the aluminum alloy substrate for a long time and toarrive at a theoretical understanding of such conditions.

Surface of the Aluminum Alloy

The desired degree of roughness for the aluminum alloy surface isobtained primarily with a strongly basic aqueous solution such as acaustic soda solution, followed by immersion in an aqueous solution ofacid and thorough rinsing with water to remove sodium ions. However,under observation with an electron microscope, the microstructure of thesurface obtained by etching with an aqueous solution of caustic soda(FIG. 5 shows an example of such a surface on A7075) has very finedepressions and protrusions with a periodicity of several tens ofnanometers. Such a surface should make a cured adhesive difficult to beremoved from depressions in the substrate; indeed, a finely irregularsurface such as this is sought after and desirable according to the NAThypothesis. Yet, on the surface obtained by immersing this aluminumalloy in an aqueous solution of nitric acid and rinsing with water (FIG.6 shows an example of such a surface on A7075), the quality required forthe fine depressions and protrusions was degraded. In short, theoperation of immersing the aluminum alloy in an acidic aqueous solutionto remove sodium ions amounted to a type of chemical polishing. Thesurface, as viewed in an electron micrograph, forms what might beexpressed in sensory terms as a textured surface. The degree of textureon this textured surface is lowered by chemical polishing, which has anopposite effect on adhesive joining.

Accordingly, the approach taken was to restore this degree of texture bythe main treatment described below. Micrographs for reference are shownin FIGS. 5 to 7, with FIG. 6 being an example of an electron micrographtaken after immersion treatment in an aqueous solution of nitric acid.The reasons explained above will be appreciated from these images. Itshould be noted that the experiences, thought and theories by theinventors which ultimately led to the present invention are also aproduct of the ability to make ready use of high-performance electronmicroscopes capable of achieving a high resolution of severalnanometers. Also, the thought in the present invention was to achievedurability and corrosion resistance of the aluminum alloy by having thefinal aluminum alloy surface be surface layer of aluminum oxide and byraising the joining strength of the adhesive to the alloy substrate tothe utmost.

[Surface Treatment, Main Treatment and Ultrafine Etching of the AluminumAlloy Part]

The aluminum alloy part on which pretreatment has been completed is thensubjected to the following type of surface treatment as the finaltreatment, i.e., main treatment. Following the completion ofpretreatment, the aluminum alloy part is immersed in an aqueous solutioncontaining at least one from among hydrazine hydrate, ammonia and awater-soluble amine compound, after which it is preferably rinsed withwater and dried at 70° C. or below. This is also intended to restore arough surface after the surface was somewhat altered by the sodiumion-removing treatment carried out as the final step in pretreatment (sothat it became smoother while retaining a degree of roughness). Thealuminum alloy part is immersed for a short time in a weakly basicaqueous solution, such as an aqueous solution of hydrazine hydrate,thereby making ultrafine etching carried out, causing the surface to becovered with a ultrafine irregular surface having depressions orprotrusions of 10 to 100 nm diameter and equal height or depth. Moreprecisely, it is desirable to form numerous fine irregularities having aperiod of 40 to 50 nm over the inner walls of the depressions in themicron-order irregularities so as to finish the surface to a high degreeof what might be referred to as texture when viewed on an electronmicrograph.

Also, by making the drying temperature after rinsing elevated to atleast 100° C., if the interior of the dryer is hermetically sealed,hydroxylation reactions between boiling water and aluminum arise,altering the surface and forming a boehmite layer. This can hardly becalled a tough surface layer and is thus undesirable. The moistureconditions within the dryer are determined not only by the size of thedryer and the manner of air circulation but also by the amount ofaluminum alloy loaded therein. In this sense, regardless of the loadingconditions, hot-air drying at 90° C. or lower, preferably at 70° C. orlower, is desirable for achieving good results having a goodreproducibility to prevent the formation of boehmite at the surface.When drying is carried out at below 70° C., only trivalent aluminum canbe detected from the aluminum peaks in surface elemental analysis byXPS; the zero-valent aluminum which can be detected in XPS analysis incommercially available A5052 and A7075 aluminum alloy plate stock andthe like vanishes.

Because XPS analysis allows elements present from the metal surface to adepth of 1 to 2 nm to be detected, these results show that immersion inan aqueous solution of hydrazine hydrate or an amine compound followedby rinsing with water and hot-air drying have the effect of making thenatural oxide layer (a thin aluminum oxide layer having a thickness ofabout 1 nm) initially present on the aluminum alloy even thicker throughthe main treatment. It was found that, unlike the natural oxide layer,the layer has a thickness of at least 2 nm, so further study was notperformed. That is, although analysis at deeper positions of from about10 to 100 nm is possible by carrying out XPS analysis after etching withan argon ion beam or the like, it was concluded that such analysis wouldbe difficult at the present time, because there is a possibility thatthe valence number of aluminum atoms in deeper layers will change due tothe influence of the beam itself. As a result, the inventors suspendedsuch inquiry.

The formation of an aluminum oxide layer on the aluminum alloy surfaceby other surface treatment methods will be discussed. One surfacetreatment method carried out to improve the durability of aluminum alloyis anodization. When anodization has been carried out on an aluminumalloy, an aluminum oxide layer having a thickness of from severalmicrons (μm) to somewhat over ten microns (μm) can be formed, greatlyenhancing durability. Innumerable openings in pits having a diameter ofabout 20 to 40 nm remain on the aluminum oxide layer immediately afteranodizing treatment. If adhesive joining or paint application is carriedout in this state, that is, in an unsealed alumite state, the adhesiveor paint will enter somewhat through the openings into the pits and becured, apparently exhibiting a strong anchoring effect and giving riseto a high joining strength in joining with an adhesive. As a matter offact, the joining of a dissimilar material with such an anodizedaluminum alloy by coating the aluminum alloy with an adhesive is knownin aircraft assembly.

However, the inventors have doubts about this. That is, when shearbreaking tests were carried out on a united object obtained by stronglyjoining together two pieces of anodized aluminum alloy using an epoxyadhesive, no sample broke with forces in excess of 40 MPa (40 N/mm²),according to the breaking tests by the inventors. Moreover, on examiningthe faces of fracture, it was not the adhesive that broke but rather, inmost cases, the anodized layer (aluminum oxide layer) was separated fromthe aluminum alloy substrate. The inventors concluded from this that,“the surface of the metal side required for strong joining must be aceramic-type high-hardness layer such as a metal oxide, while it mustnot be too thick.” Although the anodic oxide surface layer is aluminumoxide, which is an oxide of the substrate aluminum itself, the surfacelayer is a ceramic and the substrate is a metal, so the types ofmaterial are different each other.

If the ceramic material is thick, differences in the physical propertieswill necessarily emerge in an extreme state, as a result of which thematerial is likely to break. For this reason, it is preferable for themetal oxide layer to be thin. Also, it is generally understood that ifthe metal oxide is a ceramic in an amorphous or microcrystalline state,it should be joined firmly with the substrate. That is, it was concludedthat, in order to bring the shear breaking strength and tensile breakingstrength of the adhesive to a very high level of 50 to 100 MPa, themetal oxide layer should not be made so thick and that using unsealedalumite which has been anodized is undesirable.

Ultrafine Etching

What is referred to as ultrafine etching in the present invention willbe now described in further details. Upon immersion of the aluminumalloy in a weakly basic aqueous solution having a pH of 9 to 10, e.g.,hydrazine hydrate, ammonia or a water-soluble amine, at a suitabletemperature and for a suitable length of time, the entire surfacebecomes covered with ultrafine irregular shapes with depressions andprotrusions having a diameter of 10 to 100 nm. Expressed as anumber-average diameter, this is about 50 nm. Stated differently, thismeans that it is desirable to select a pH, temperature and time whichare optimal for obtaining ultrafine topographically irregular shapeshaving a diameter of 10 to 100 nm on the surface. Based on experience,the inventors predict that the ultrafine irregularities with depressionsand protrusions have a period or a diameter, which is most preferablyabout 50 nm. The reason is that, in the case of irregularities having aperiod of 10 nm, rather than being a textured surface, the manner ofirregularity is too fine, resulting in a surface that is smooth for anadhesive. On the other hand, a period of more than 100 nm appears toexceed the bounds of what would normally be construed as a texturedsurface, so that there is little inclination to anchoring. In thepresent invention, “number average” does not refer to a mean ofsummation of a degree that enables statistical validation but, rather,it refers to an average value obtained for 20 or fewer samples.

The value of 50 nm was obtained at empirically based on experimentalresults. However, even when aiming at a period of 50 nm, a perfectlyordered arrangement cannot be obtained with chemical reactions, so somevariability is to be expected. There is no alternative but to examinephotographs taken with an electron microscope and convert the resultantinto numerical values. The result corresponds to a surface of ultrafineirregular shapes that are substantially entirely (100%) covered with 10to 100 nm diameter depressions and protrusions of the same depth orheight. In fact, when most of the surface was occupied by depressions orprotrusions having a diameter of 10 to 20 nm, or, conversely, bydepressions and protrusions having a diameter of 100 nm or more, thejoining strength was inferior. Actual cases, in which A7075 material orA5052 material was etched with an aqueous solution of hydrazine hydrate,will be described below in the following experimental examples.

Experimental Examples of Ultrafine Etching

In order to be able to cover an aluminum alloy with depressions andprotrusions of such a size, it is necessary to search for the immersionconditions by trial and error. When a 60° C. aqueous solution containinga hydrazine monohydrate concentration of 3.5% is used to immerse A5052and A7075 stock, setting the immersion time to about 2 minutes isoptimal. The surface obtained from this immersion time is coveredentirely with depressions having a diameter of 10 to 100 nm, thenumber-average diameter being 40 to 50 nm. However, when the stock isimmersed for 4 minutes, the diameter of the depressions rises to 80 to200 nm, the number-average diameter is increased suddenly to more than100 nm and additional depressions are formed at the bottom of thesepits, making the structure more complex. In addition, when the stock isimmersed for 8 minutes, erosion in the form of lateral holes alsoproceeds, resulting in somewhat of a sponge-like shape, in addition towhich deep depressions are interconnected, changing into a valley orravine-like shape. With 16 minutes of immersion, the aluminum alloyvisibly changes from the original metal color, becoming somewhatbrownish, from which it is apparent that the manner in which visiblelight is absorbed has begun to change.

When the immersion time under the above conditions was one minute,depressions having a diameter of 10 to 40 nm were observed with electronmicrographs. The number-average diameter of these depressions was 25 to30 nm. In addition, with 0.5 minute of immersion, the depressionscovering the surface had a diameter of 10 to 30 nm, the number-averagediameter for these depressions being about 25 nm, which is not sodifferent from the results for an immersion time of one minute. Electronmicrographs of an aluminum alloy immersed for 0.5 minute and an aluminumalloy immersed for one minute were carefully compared, whereupon thedepth of the depressions was clearly shallower in the alloy immersed for0.5 minute than in that immersed for one minute. Thus, in A5052 andA7075 stock immersed in a weakly basic aqueous solution, erosion beginsat a period of 20 to 25 nm, with depressions having a diameter of 20 nmfirst being formed for some unknown reason. When the depth of thesedepressions has been increased to about the same level as the diameter,the edges of the depressions are then eroded, the depression diameter isincreased and erosion in indefinite directions at the interior of thedepressions begins. When erosion has taken place in this way, the simpleand robust erosion that is most suitable for adhesive joining wasachieved with immersion of the A7075 or A5052 in a 3 to 5%-aqueoussolution (60° C.) of hydrazine monohydrate for about 2 minutes.

A resultant obtained, for example, by use of the one-pack,high-temperature curing epoxy adhesive EP106 (available from Cemedine,Japan) having a viscosity of 40 Pa·s at a temperature of 23° C., will bedescribed. Based on the results of the adhesion experiments shown in theworking examples, in the case of an aluminum alloy stock such as A7075that was immersed for one minute in an aqueous solution of hydrazinehydrate under the conditions mentioned above, the fine depressions had anumber-average diameter of about 25 nm, which was too small and theepoxy resin appeared to have difficulty in entering into these finedepressions. The joining strength apparently reached a maximum value incases where the immersion time was set to two minutes. When A7075, etc.was immersed for two minutes under the above-mentioned conditions, thefine depressions had a number-average diameter of about 40 nm; thisepoxy resin would presumably have been able to make its way into theinterior of fine depressions of at least about this size.

In short, when the inner surfaces of micron-order depressions aretextured faces having irregularities with depressions and protrusions ata period of several tens of nanometers, the joining strength rises.Also, when the above-described immersion time is longer than 2 minutes,e.g., when it is extended to 4 minutes or 8 minutes, not only is thedepression diameter increased but also other depressions are formedwithin the depressions, resulting in what could be characterized as asponge-like shape. Thus, not only is the strength of the aluminum alloysurface layer itself weakened but also the adhesive is unable topenetrate all the way into the back of the complex holes. As a result,the number of voids at the joining interface of the joined object isincreased, resulting in a joining strength that is lower than themaximum value. In short, when the above-mentioned epoxy adhesive is usedfor an aluminum alloy such as A7075, in addition to providing a suitablemicron-order roughness, it is desirable to cover the surface withultrafine depressions having a number-average diameter of 40 to 50 nm,in order to maximize the joining strength. It can be appreciated thatthe range in the optimal immersion time for creating such ultrafinedepressions is very narrow. This is because the best joining resultswere obtained at an immersion time of about 2 minutes as mentionedabove.

When the same epoxy adhesive was used on A5052 aluminum alloy, theimmersion conditions during etching in an aqueous solution of causticsoda differed somewhat from those for A7075. Obviously, this is probablydue to differences in the manner of erosion and in the properties of theeroded surface. Further details will be given in the subsequentlydescribed experiment examples.

Ammonia water has a lower pH than an aqueous solution of hydrazine and,when the aqueous solution is set to a temperature higher than standardtemperature, evaporation of the ammonia becomes vigorous. For thesereasons, such immersion treatment is carried out at a high concentrationand a low temperature; even when very strong ammonia water having aconcentration of about 25% is used, an immersion time of 15 to 20minutes is required. Conversely, most water-soluble amines form aqueoussolutions having a stronger basicity than aqueous solutions ofhydrazine, so the period of treatment will be shorter. In massproduction treatment, the stability of the operation is lost if theimmersion time is too long or too short. In this sense, the use ofhydrazine hydrate, which allows the optimal immersion time to be set toseveral minutes, appears to be suitable for practical purposes.

In all cases, there were types of alloys for which the joining strengthwas improved upon immersion in an aqueous solution of hydrogen peroxideof several percent concentration following immersion in an aqueoussolution of hydrazine hydrate, ammonia or a water-soluble amine. Thethickness of the metal oxide layer on the surface may be increased butanalysis is difficult at thicknesses greater than 2 nm, makingtheoretical elucidation impossible.

[Epoxy Resin-Based Adhesives and their Application]

A commercially available epoxy resin for adhesives may be used as theinitial material for the epoxy-based adhesive employed in the presentinvention. Commercially available epoxy resins for adhesives include,for example, bisphenol-type epoxy resins, glycidyl amine-type epoxyresins, polyfunctional polyphenol-type epoxy resins and alicyclic epoxyresins. Any of these types may be used in the present invention.Alternatively, use may be made of a product obtained by couplingtogether these epoxy resins via reaction with a polyfunctional thirdingredient, such as a polyfunctional oligomer having a plurality ofhydroxyl groups. It is preferable to add a polyfunctional amine compoundas a curing agent to these epoxy resins for adhesives and mix thosetogether so as to create a one-pack epoxy adhesive.

Elastomer Ingredient

Adding an elastomer ingredient or the like to the above-mentionedepoxy-based adhesive ingredients is desirable in that a cushioningmedium can be obtained for the situation where the joint is subjected totemperature shock or physical shock. Also, the addition of filleringredients to the above ingredients is advantageous for enabling thelinear expansion coefficient to be matched to that of the aluminum alloyand that of the CFRP material. The elastomer ingredient is preferablyincluded in an amount of from 0 to 30 parts by weight per 100 parts byweight of the above resin ingredients combined (epoxy resiningredients+curing agent ingredients). Including an excessive amount ofthe elastomer ingredient of more than 30 parts by weight will lower thejoining strength, which is undesirable. One of the elastomer ingredientsis a vulcanized rubber powder having a particle size of from severalmicrons to 15 μm. Even when the adhesive is applied, the particles witha particle size of several microns or more are somewhat too large toenter the depressions on the aluminum alloy. As a result, they remainentirely in the adhesive layer and have no influence on the anchoringareas.

As a result, this ingredient has a role of withstanding shock without aloss of joining strength. Various types of vulcanized rubber may beused, although, regardless of the type of rubber, milling to amicron-order particle size is difficult. To the extent of theinvestigations conducted by the inventors, perhaps owing to a lack ofneed, there appears to be no sign of any research and development havingbeen actively carried out on methods for manufacturing vulcanized rubberin the form of fine particles. The inventors tried the method of coolinga natural rubber vulcanizate (an ingredient which is substantially thesame as the ingredient formulated in tire rubber, excluding carbonblack) with liquid nitrogen, followed by mechanical milling andclassification. Unfortunately, the product costs are not within a realmthat is commercially viable. Another approach was to use unvulcanized orsemi-crosslinked rubber and a modified super engineering plastic or apolyolefin resin. An exemplary modified super engineering plastic is thehydroxyl-terminated polyether sulfone PES100P (available from MitsuiChemical, Japan). That is, use may be made of end-modified thermoplasticresins of a hydroxyl-terminated polyether sulfone which have a meltingpoint or softening point of at least 300° C.

Polyolefin resins which mix easily with epoxy resins have already beendeveloped and may also be advantageously used. The inventors believe thedurability against temperature shock to be theoretically inferior tothat of powdered vulcanized rubber but this is not yet in fact wellknown. The evaluation techniques themselves have not been carried out tothe limit in the methods by the inventors. In any case, even theadmixture of such unvulcanized elastomers was found to result in a highstrength to temperature shock. Examples of such polyolefin resinsinclude maleic anhydride-modified ethylene copolymers, glycidylmethacrylate-modified ethylene copolymers, glycidyl ether-modifiedethylene copolymers and ethylene alkyl acrylate copolymers.

Filler

In addition, the filler will be described. It is preferable to use anepoxy adhesive composition which additionally contains from 0 to 50parts by weight of filler per 100 parts by weight of total resiningredients including elastomer ingredient. Examples of fillers includereinforcing fiber-type fillers such as carbon fibers, glass fibers andaramid fibers; and powder-type fillers such as calcium carbonate, mica,glass flakes, glass balloons, magnesium carbonate, silica, talc, clayand crushed carbon fibers or aramid fibers. Carbon nanotubes may also beused as filler.

Preparation of Epoxy Adhesive

Preparation of the epoxy adhesive entails thoroughly mixing together themain epoxy resin ingredients, elastomer, filler and curing agent andalso, depending on the viscosity, mixing a solvent for epoxy adhesives(which is also commercially available). In the present invention, thismixture serves as an adhesive composition (an uncured epoxy resincomposition). This adhesive composition is applied to the necessaryplaces on the aluminum alloy part obtained in the preceding step. Eithermanual application with a brush or application with an adhesive coatingequipment may be adopted.

[Treatment Step Following Application of Epoxy Resin Adhesive]

After coating, it is preferable to place the coated piece in a vacuumvessel or a pressure vessel, reduce the pressure almost to vacuum, holdthe piece in this state for several minutes and then, by introducingair, either return the pressure to standard pressure or apply a pressureof several atmospheres or several tens of atmospheres. In addition,repeated cycling with raising and lowering of pressure is alsoadvantageous. In this way, air and gases between the coating materialand the aluminum alloy are removed, facilitating penetration of theapplied material into the ultrafine depressions. In actual massproduction, using a pressure vessel and high-pressure air leads toincreased costs, both in respect of equipment and operatingexpenditures, so it is economically effective to carry out one orseveral cycles of pressure reducing/standard pressure restoration orpressure reducing/pressurization to several atmospheres using a vacuumvessel. Using the aluminum alloy according to the present invention, asufficiently stable joining strength can be achieved with several cyclesof pressure reducing/normal pressure restoration. It is also desirableto then remove the workpiece from the vessel and let it to stand forseveral hours in an environment of normal temperature or atapproximately 40° C. Even in cases where some solvent has been added tothe epoxy adhesive composition, this will enable most of the solvent tobe vaporized off.

[FRP Prepreg]

Fiber-reinforced plastics (FRP) are exemplified by glassfiber-reinforced plastics (abbreviated below as GFRP), aramidfiber-reinforced plastics (AFRP) and CFRP. In this specification, FRPsin which epoxy resin serves as the matrix are discussed, while any typeof FRP may be employed in the present invention, including those usingglass fibers, carbon fibers or aramid fibers, as well as those which useother reinforcing fibers. The description that follows relatesspecifically to CFRPs, in which the effects of the present invention aremost readily apparent. On the other hand, specific description of otherFRPs will be omitted.

Use of a commercially available CFRP prepreg may be done, of course.Commercially available products sold as prepregs include carbon fiberwoven cloth impregnated with the above-mentioned epoxy-based adhesiveand prepregs produced by creating a film-like material from theabove-mentioned epoxy resin in uncured form and laminating the materialwith a carbon fiber woven cloth. Such techniques are known in common andany person with ordinary skill in the art, not limited only tospecialized manufacturers, could easily fabricate a prepreg using acarbon fiber woven fabric and a one-pack epoxy-based adhesive. Epoxyresins commonly used for this purpose include dicyandiamide-curableepoxy resins and amine-curable epoxy resins. Such resins are designed tomaintain a B stage (a nearly solid but uncured state) at normaltemperature, melt in the course of temperature rise to somewhere inexcess of 100° C. and be cured thereafter. In this sense, it ispreferable that the epoxy-based adhesive coated onto the aluminum alloypart and the epoxy-based uncured resin (adhesive) used in the CFRPprepreg have identical curing temperature properties. However, inexperiments by the inventors, a high joining strength was obtained evenwith a prepreg that was heat-cured without particular adjustment ofthese curing temperature properties. It may thus be possible to obtaineven better united object by carrying out further detailedinvestigations.

The uncured prepreg is cut into the required shape and stacked in therequired manner to prepare the prepreg portion. That is, when aplurality of sheets of a unidirectional prepreg (a prepreg composed of acloth woven from many warp threads but very few filling threads) arestacked to form a plate-like laminate, the strength directionality ofthe finished laminate can be controlled, by stacking the fabric with thefilaments oriented in the same direction or at differing angles. Inthis, there appears to be much know-how on the assembly of suchprepregs. Also, it is reported that, the number of warp threads and thenumber of filling threads is the same in a carbon fiber plain-wovencloth and, when prepregs are stacked while changing the angle 45 degreesin each successive layer, the final CFRP laminate will have the samestrength in all directions. Hence, the required number of layers and themanner of stacking are planned preliminarily, then each prepreg is cutand stacked according to the plan to complete the laminate.

[Method for Layering the Prepregs and Manufacturing the Composite]

The above FRP prepreg (plate-like laminate) is placed on the earlierdescribed epoxy adhesive-coated aluminum alloy part. When heated in thisstate, the epoxy resin adhesive and the epoxy resin in the prepreg melt,following which they are cured. For strong joining, it is necessary forheating to be carried out in a state where the prepreg and the aluminumalloy part are pressed together and for air present therebetween to beexpelled during melting of the resin. For example, by prefabricating aseat which matches the shape of the face of the aluminum alloy on theside opposite to the joining face thereof, laying some aluminum foil orpolyethylene film down on the seat, then setting the aluminum alloy parton the foil or film, placing the prepreg on the aluminum alloy part,laying polyethylene film on top of the prepreg, placing thereon aseparately fabricated member to be fixed thereto that was separatelyfabricated from structural stock or the like and matched to the prepregshape of the finished product and setting a weight on top, pressing andfixing can be carried out during hot curing.

Of course, any of various methods other than gravity alone may beutilized to induce curing while pressing both sides together. In thecase of a member of aircraft, the entire assembly described above isenclosed in a film bag, then overheated while lowering the pressure,thereby forcibly drawing out air from the interior when all the epoxycomponent has melted. Because the prepreg tightens when the air has beendrawn out to a certain degree, air is subsequently supplied into thefilm bag, thereby inducing curing under increased pressure in thisarrangement. Experiments were carried out here under the assumption thatthe air within the prepreg is drawn off substantially by the mechanicalpressure applied during melting of the epoxy component.

Heating is carried out by placing the above overall assembly in ahot-air dryer or an autoclave. Generally it is preferable to hold theassembly at between 110 and 140° C. for several tens of minutes, therebycausing the adhesive component to melt and inducing gelation, then raisethe temperature to between 150 and 170° C. and heat for another severaltens of minutes to effect curing. The optimal temperature conditionsvary depending on the epoxy component and the curing agent component.After curing, the assembly is allowed to be cooled, then the metallicmold is removed and the shaped object is taken out. When aluminum foilor polyethylene film are used as described above, these are peeled offto enable the object to be released from the mold.

Method of Measuring Joining Strength

Measurement of the joining strength between the aluminum alloy and theFRP used in the present invention will be described below. FIG. 1 is asectional view of a firing jig for joining the aluminum alloy and theFRP together. FIG. 2 shows a test piece of an aluminum alloy composite10 fabricated by firing the aluminum plate and CFRP in the firing jig 1.The firing jig 1 is a holder for immobilizing the aluminum alloy plate11 and the prepreg 12 when they are fired. The metallic mold body 2 isopen at a top surface thereof and has formed therein a recessed portion3 of rectangular shape. A mold throughhole 4 is formed at the bottomthereof.

A bottom plate projection 6 on a mold bottom plate 5 is inserted intothe mold throughhole 4. The bottom plate projection 6 extends out fromthe mold bottom plate 5 on the mold body 2. The mold body 2 is mountedon top of a mold seat 8 with the bottom face 7 mating with the seat 8.In the situation where the mold bottom plate 5 is inserted and placedwithin the recessed portion 3 of the mold body 2, an aluminum alloycomposite 10 composed of an aluminum alloy plate 11 joined with CFRP 12as shown in FIG. 2 is produced through firing. Briefly, production ofthis aluminum alloy composite 10 is carried out by the followingprocedure. First, a mold release film 17 is laid down over the entireupper face of the mold bottom plate 5. An aluminum alloy plate 11 and aplate-like PTEF spacer 16 are set on top of the mold release film 17. Arequired prepreg 12 is placed on this PTEF spacer 16 and along with iton top of an end of the aluminum alloy plate 11. The prepreg 12 is aCFRP prepreg composed of a reinforcing fiber woven cloth impregnatedwith an uncured epoxy-based adhesive.

After laying down the prepreg 12, a piece of mold release polyethylenefilm 13 is additionally placed on both the aluminum alloy plate 11 andthe prepreg 12. Then, PTEF blocks 14 and 15 of PTEF(polytetrafluoroethylene resin) are set on top thereof as weights. Inaddition, where necessary, weights of several hundred grams (not shown)are placed on top of the blocks. The resulting assembly is loaded inthis state into a firing oven, where the prepreg is cured, then allowedto be cooled. The weights, seat 8 and the like are then removed and, bypushing the bottom end of the bottom plate projection 6 against thesurface of the floor below, the aluminum alloy composite 10 (see FIG. 2)obtained by joining the aluminum plate with the CFRP can be removedtogether with the mold release films 13 and 17. The PTEF spacer 16 andthe mold release films 17 and 13, being made of non-stick materials, canthen be easily peeled from the CFRP.

[Examples of Methods for Using Composites]

FIG. 3 is a partial solid view showing an example in which an aluminumalloy/FRP composite according to the present invention and a metalstructural material (angle bar) are joined together using bolts andnuts. The aluminum alloy composite 20 is a composite obtained by unitingan aluminum alloy with CFRP. The CFRP 21 is a plate-like structureproduced by firing the prepreg. The angle bar 23 is a prefabricatedstructural material. Rectangular reinforcing plates 22 are integrallyjoined with the front and back sides of the CFRP 21. The reinforcingplates 22 are made of aluminum alloy (e.g., A7075) and have been firedand integrally joined beforehand with the CFRP 21 by the above-describedmethod.

The CFRP 21, the reinforcing plates 22 on the front and back sidesthereof and the angle bar 23 are fastened together so that no movementoccurs therebetween by means of a bolt 25 along with a nut placed on theunderside of the angle bar 23 (not shown) through an upper washer 24placed on the reinforcing plate 22 and a lower washer (not shown) placedon the bottom face of the angle bar 23. In the aluminum alloy composite20 obtained by joining together rectangular plates 22 made of aluminumalloy (A7075) and CFRP 21, the joining strength between both materialsis extremely high, the shear breaking strength being from 50 to 70 MPa.Moreover, the forces applied to the plates 22 by the bolt 25 and washer24 or the like can be effectively dispersed on the CFRP 21. In short,even when the bolt 25 and nut are tightened with sufficient strength,only the plates 22 made of A7075 are deformed; the CFRP 21 in thecomposite 20 is not damaged. An aluminum alloy and CFRP can be stronglyjoined by the method for manufacturing an aluminum alloy compositeaccording to the present invention as stated above.

As described in detail above, in the aluminum alloy composite and methodfor manufacturing thereof according to the present invention, analuminum alloy part and FRP are strongly united, thereby enabling tough,lightweight components to be produced. Because parts obtained byintegrally uniting an aluminum alloy member with an FRP member can bemanufactured as parts for aircrafts and other applications, novelconstructions may be employed when the need arises to join and fastenboth materials.

Also, because the aluminum alloy composite according to the presentinvention is light, it can be employed in components for vehicles, suchas parts for automotives and parts for bicycles, where lighter weight isstrongly desired. That is, because the aluminum alloy stock can beformed in a relatively free shape by mechanical working or the like,existing fastening methods such as a bolt-and-nut technique or ascrewing technique can be employed to join two pieces of aluminum alloy.FRP parts, on the other hand, are suitable for forming objects withplate-like or pipe-like shapes rather than complex shapes and even makeit possible to create large or elongated cured objects. As a result,composite structures can be produced which exhibit the characteristicsof both materials.

Hence, by having the end of a integrally united part made of aluminumalloy, it is possible to arrive at a member capable of being easilyassembled with nuts and bolts or with screws. In summary, by preciselydesigning the surface of the aluminum alloy, the joining strength andaccuracy in joining with the epoxy resin can be made vastly high, makingit possible to employ new methods of fabrication and assembly thatutilize such joining strength.

Embodiments of the present invention will be described below by means ofexperiment examples. FIG. 4 shows the configuration in which two piecesof aluminum alloy are joined together with an adhesive (metal on metal).In the figure, aluminum alloy piece 30 and aluminum alloy piece 31 arealuminum alloy plates made of the same material respectively. Aluminumalloy piece 30 and aluminum alloy piece 31 are joined at a joining face32. At this joining face 32, as described above, a micron-order surfaceroughness is formed by chemical etching at the surface. This surface hasa thin layer of sodium ion-free aluminum oxide with a thickness of atleast 2 nm and the interior of the surface roughness is covered by anultra fine irregular surface with depressions and protrusions having adiameter of 10 to 100 nm and the same depth or height.

It is to these ultrafine irregular surfaces that joining has taken placethrough an intervening epoxy-based adhesive. FIG. 2 shows a test piecefor measuring the joining strength obtained when an aluminum alloy plateand FRP are joined together with an epoxy-based adhesive. As explainedabove, FIG. 3 is a schematic view for a case in which a compositeobtained by joining an aluminum alloy plate and FRP with epoxy resin isconnected with another metal part by means of bolts and nuts. Specificworking examples will be described subsequently. The followinginstruments were used for obtaining measurements.

(a) X-Ray Surface Examination (X-Ray Photoelectron Spectroscopy (XPS))

An ESCA spectrometer (AXIS-Nova, manufactured by Kratos/ShimadzuCorporation, Japan) was used to examine the constituent elements on asurface of several micrometers in diameter to a depth of 1 to 2 nm.

(b) Electron Microscopic Examination

Observation was carried out at 1 to 2 kV using scanning electronmicroscopes (SEM) (S-4800, manufactured by Hitachi, Ltd., Japan) andJSM-6700F (JEOL, Japan).

(c) Scanning Probe Microscopic Examination

A SPM-9600 (Shimadzu Corporation, Japan) was used.

(d) X-Ray Diffraction Analysis (XRD Analysis)

An XRD-6100 (Shimadzu Corporation, Japan) was used.

(e) Measurement of Joining Strength in Composite

Using a tensile testing machine (Model 1323, manufactured by AikohEngineering, Japan), the shear breaking strength was measured at atension speed of 10 mm/min.

WORKING EXAMPLES Experiment Example 1 Adhesion with A5052 Aluminum Alloy

Commercially available A5052 sheet stock having a thickness of 1.6 mmwas acquired and cut to form a plurality of rectangular pieces measuring45×18 mm. Water was made ready in a tank and a commercially availablealuminum alloy degreaser (NE-6, available from Meltex, Japan) was addedto the water to form a aqueous solution of 60° C. having a concentrationof 7.5%. The rectangular pieces of aluminum alloy were immersed in thesolution for 7 minutes and then thoroughly rinsed with water. An aqueoussolution of hydrochloric acid having a concentration of 1% and adjustedto 40° C. was made ready in another tank, in which the aluminum alloypieces were immersed for 1 minute and then thoroughly rinsed with water.Next, an aqueous solution of caustic soda having a concentration of 1.5%and adjusted to 40° C. was made ready in still another tank, in whichthe same aluminum alloy pieces were immersed for 2 minutes and thenthoroughly rinsed with water. An aqueous solution of nitric acid havinga concentration of 3% and adjusted to 40° C. was made ready in yetanother tank, in which the aluminum alloy pieces were subsequentlyimmersed for 1 minute and then rinsed with water.

Next, an aqueous solution containing hydrazine monohydrate by 35% andadjusted to 60° C. was made ready in another tank, in which the aluminumalloy pieces were immersed for 1 minute, rinsed with water and thendried by being placed in a hot-air dryer set at 67° C. for 15 minutes.After drying, the aluminum alloy pieces were collected together, wrappedwith aluminum foil and then placed in a plastic bag, which was closedand stored. Four days later, one of the pieces was examined with anelectron microscope and found to be covered with depressions ofdiameters ranging from 10 to 80 nm and a number-average diameter of 25to 30 nm.

This is shown in the micrograph of FIG. 9. Another piece was examinedwith a scanning probe microscope, with which the piece was scanned overa length of 20 μm at 40 μm/s, and the mean peak spacing (RSm) andmaximum height (Rz) according to JIS B 0601: 2001 were measured,yielding respective results of 1.1 μm (RSm) and 0.3 μm (Rz). FIG. 15shows these roughness curves. In addition, still another piece wassubjected to examination with XPS and aluminum atoms were observed. Incontrast with the purchased A5052, which was observed to have a ratio ofzero-valent aluminum to trivalent aluminum of about 1:3, the piece, forwhich surface treatment was carried out, showed no sign of zero-valentaluminum and the thickness of the aluminum oxide layer had increased.Because the atomic composition to a depth of up to 1 to 2 nm from thesurface was detected in XPS, it was apparent that the aluminum oxidesurface layer had a thickness of more than 2 nm.

The same day, ten pieces of aluminum alloy for which surface treatmenthad been performed as described above were taken out and lightly coatedon the ends with a commercially available liquid-type one-packdicyandiamide-curable epoxy adhesive (EP-106, available from Cemedine,Japan). The pieces were placed in a desiccator with the coated sidefacing upward, the desiccator was evacuated with a vacuum pump to 1 mmHgand left in this state for one minute, following which air wasintroduced, returning the interior to standard pressure. This operationof reducing the pressure and then returning to standard pressure wasrepeated three times, following which the pieces were removed from thedesiccator. The pieces were transferred to the interior of a hot-airdryer and assembled into five pairs by stacking two pieces with theadhesive-coated sides mating with one another so that each joined facearea was about 0.5 cm², a weight of 500 g was placed at each joinedface, the door was closed and the temperature was rapidly raised to 135°C. Forty minutes later, the hot-air dryer setting was changed to 165° C.and the rise in temperature was awaited. Once the temperature reached165° C., this state was held for 20 minutes, then the power on thehot-air dryer was turned off, the door of the dryer was opened and theinterior was allowed to be cooled. By means of this operation, as shownin FIG. 4, united test pieces composed of a first aluminum alloy piece30 and a second aluminum alloy piece 31 joined at the joining face 32respectively were obtained. Two days later, the test pieces weresubjected to tensile breaking tests, whereupon the average shearstrength at break for the five pairs was 48 MPa, which was very strong.

Experiment Example 2 Adhesion with A5052 Aluminum Alloy

Surface treatment for pieces of A5052 plate was carried out in the sameway as Experiment example 1. Up through treatment with the degreaser(NE-6, available from Meltex, Japan), preliminary pickling treatmentwith a 1%-aqueous solution of hydrochloric acid and alkali etchingtreatment with a 1.5%-aqueous solution of caustic soda, treatment wascarried out in exactly the same as in Experiment example 1. Surfacetreatment ended at this point and the pieces were stored in theresulting state. The same day, these aluminum alloy pieces were takenout, the epoxy adhesive EP-106 was lightly coated on the ends anddesiccation treatment, joining and curing of the adhesive in a hot-airdryer were subsequently carried out in exactly the same way as inExperiment example 1, yielding the test pieces shown in FIG. 4.

In tensile failure tests carried out two days later, the average shearstrength at break for the four pairs was 48 MPa. These test pieces thusexhibited the same high joining strength as in Experiment example 1. Thealuminum alloy pieces following surface treatment were subjected to XPSanalysis, where large peaks for oxygen and aluminum were observed andsmall peaks for magnesium, zinc and sodium were also noted. In thisexperiment example, in which surface treatment ended with treatment inan aqueous solution of caustic soda, it was shown that sodium ions arenot removed by rinsing with water alone.

Experiment Example 3 Adhesion with A5052 Aluminum Alloy

Pieces of A5052 plate were treated in the same way as Experiment example1 up to a given point. Up through treatment with the degreaser NE-6,preliminary pickling treatment with a 1%-aqueous solution ofhydrochloric acid, alkali etching treatment with a 1.5%-aqueous solutionof caustic soda and neutralization treatment with a 3%-aqueous solutionof nitric acid, treatment was carried out in exactly the same as inExperiment example 1. Surface treatment ended at this point and thepieces were stored in this state.

When these aluminum alloy pieces were subjected to XPS analysis, peaksfor sodium were not observed, even cumulatively. Hence, sodium wasconcluded to have been removed by immersion in the aqueous nitric acidsolution and rinsing with water. The same day, these aluminum alloypieces were taken out, the epoxy adhesive EP-106 was lightly coated onthe ends and desiccation treatment, joining and curing of the adhesivein a hot-air dryer were subsequently carried out in exactly the same wayas in Experiment example 1. In tensile breaking tests carried out twodays later, the average shear strength at break for the four pairs was44 MPa. The joining strength was somewhat lower than in Experiments 1and 2.

Experiments Example 4 to 12 Adhesion with A5052 Aluminum Alloy

In Experiment examples 4, 5 and 6, surface treatment up to immersion inan aqueous solution of hydrazine hydrate was carried out in the same wayas in Experiment 1. Compared with Experiment example 1, only theimmersion times in the aqueous solution of caustic soda were madedifferent. These immersion times were 1 minute in Experiment example 4,2 minutes in Experiment example 1, 4 minutes in Experiment example 5 and8 minutes in Experiment example 6. In Experiment examples 7, 8 and 9,surface treatment up to immersion in an aqueous solution of caustic sodawas carried out in the same way as in Experiment example 2. Comparedwith Experiment 2, only the immersion times in the aqueous solution ofcaustic soda were made different. These immersion times were 1 minute inExperiment example 7, 2 minutes in Experiment example 2, 4 minutes inExperiment example 8 and 8 minutes in Experiment example 9.

In Experiments examples 10, 11 and 12, surface treatment up to immersionin an aqueous solution of nitric acid soda was carried out in the sameway as in Experiment example 3. Compared with Experiment example 3, onlythe immersion times in the aqueous solution of caustic soda were madedifferent. These immersion times were 1 minute in Experiment example 10,2 minutes in Experiment example 3, 4 minutes in Experiment example 11and 8 minutes in Experiment example 12. The results for Experimentexamples 1 to 12 are shown in Table 1. The same results are plotted asgraphs in FIG. 13. The ordinate represents the adhesive strength betweenthe A5052 aluminum alloy pieces and the abscissa represents theimmersion time in a 1.5%-aqueous solution of caustic soda.

TABLE 1 Shear strength at break of A5052. Immersion time in 1.5%-causticsoda solution Treatment step 1 minute 2 minutes 4 minutes 8 minutes (1)Up to Experiment Experiment Experiment Experiment caustic soda example 7example 2 example 8 example 9 treatment Joining 32 Mpa 48 Mpa 45 Mpa 35Mpa strength (2) Up to Experiment Experiment Experiment Experimentneutralization example 10 example 3 example 11 example 12 treatmentJoining 20 Mpa 44 Mpa 41 Mpa 40 Mpa strength (3) Up to ExperimentExperiment Experiment Experiment hydrazine example 4 example 1 example 5example 6 treatment Joining 29 Mpa 48 Mpa 45 Mpa 36 Mpa strength

As is apparent from FIG. 13 and Table 1, using a combination of A5052treated with a 1.5%-aqueous solution of caustic soda and epoxy resincomposition EP-106, the highest joining strength is obtained at animmersion time of about 2 minutes in the aqueous solution of causticsoda. What is distinctive here is that, among the test pieces which wereimmersed for 2 minutes in an aqueous solution of caustic soda, theproduct etched with caustic soda (Experiment example 2) and the productobtained by subsequent neutralization as well as hydrazine treatment(Experiment example 1) exhibited substantially the same level of joiningstrength. Of the treated products in which sodium ions were not present,those subjected to treatment up to hydrazine treatment exhibited thehighest adhesive strength.

Also, in cases where the immersion time in an aqueous solution ofcaustic soda was 8 minutes, etc., when the A5052 aluminum alloy pieceswere etched too long, the product treated up to neutralization(Experiment example 12) had the highest joining strength. In comparingthe product obtained by surface treatment up to immersion in a causticsoda solution with the product obtained by surface treatment up toimmersion in a hydrazine solution, the results were reversed. Longimmersion in an aqueous solution of caustic soda resulted in a roughnessperiodicity of several microns, with little difference in the perioditself. However, the depth and height difference were changeddrastically (based on examination with scanning probe microscope) andlateral holes even formed, resulting in an excessively complex surfaceshape which was thought to have weakened the joining strength.

Because neutralization treatment is a step that actually involvesimmersion in an acidic aqueous solution, aluminum alloy, being anamphoteric metal, dissolves slightly even in acidic water; inparticular, protruding portions reportedly dissolve easily particularlyin an acidic aqueous solution. Therefore, it is considered thatExperiment example 12 exhibited a better adhesive strength than inExperiment example 9 because the excessively complex roughness wasleveled out somewhat, returning to a suitable degree of roughness.

Experiment Examples 13 to 15 Adhesion with A5052 Aluminum Alloy

Joining/breaking experiments were carried out in the same way as inExperiment example 1. However, unlike in Experiment example 1, theimmersion time in the 1.5%-aqueous solution of caustic soda was set to 2minutes, the best time in Experiment examples 1 to 12 and the immersiontime in the 3.5%-aqueous solution of hydrazine hydrate was varied in therange of 1 to 8 minutes.

That is, the immersion time was set to 1 minute in Experiment example 1,2 minutes in Experiment example 13, 4 minutes in Experiment example 14and 8 minutes in Experiment example 15. The results are shown in Table 2and FIG. 14.

TABLE 2 Shear strength at break of A5052 (with 2 minutes immersion in1.5%-aqueous caustic soda) Hydrazine hydrate immersion time 1 minute 2minutes 4 minutes 8 minutes Experiment Experiment Experiment Experimentexample 1 example 13 example 14 example 15 Joining 48 Mpa 60 Mpa 41 Mpa28 Mpa strength

As shown in Table 2 and FIG. 14, the highest joining strengths wereobtained with an immersion time of 2 minutes in an aqueous solution ofhydrazine hydrate. Examination of the surface with an electronmicroscope showed that the entire surface was covered with depressionshaving a diameter ranging from 20 to 100 nm and a number-averagediameter of 40 to 50 nm. A joining force of 60 MPa (about 600 kgf/cm²)corresponds to a breaking force of 300 kgf for an object having ajoining face area of 0.5 cm². FIGS. 9, 10, 11 and 12 show electronmicrographs of the A5052 aluminum alloys obtained in Experiment examples1, 13, 14 and 15 at magnifications of 10,000 times and 100,000 timesrespectively. It can be seen from these that, as the immersion timeincreases, the finely textured surface becomes more complex, in thiscase the diameter of the fine depressions becomes larger and otherdepressions are formed within the earlier formed depressions, leading toa rapid decline in the strength of the surface layer itself on thealuminum alloy.

It will be appreciated that, on a surface like that shown in theelectron micrograph of FIG. 12, a viscous epoxy-based adhesive will beunable to penetrate deep into the complex fine depressions. Further, onexamining the same aluminum alloy piece as used in Experiment example13, for which the highest joining strength was exhibited, with ascanning probe microscope, the mean roughness period (this is the sameas the mean peak spacing RSm according to JIS) was 1.2 μm and themaximum height (Rz) was 0.5 μm.

Experiment Example 16 Adhesion with A5052 Aluminum Alloy

As in Experiment example 13, pieces of A5052 sheet stock were degreasedand rinsed with water, subjected to preliminary pickling and rinsed withwater, etched with an aqueous solution of caustic soda and rinsed withwater, neutralized with an aqueous solution of nitric acid and rinsedwith water, then finely etched with an aqueous solution of hydrazinemonohydrate and rinsed with water. Next, the pieces for which surfacetreatment was performed were placed in a hot air dryer set to 150° C.for 15 minutes and dried. That is, while the drying temperature inExperiment example 13 was set to 67° C., the wet A5052 following rinsingwas directly loaded at an elevated temperature of 150° C. and dried inthis experiment example. This is the difference with Experiment example13.

Exactly the same procedure as in Experiment example 1 was subsequentlyfollowed. Using the epoxy adhesive EP-106, two pieces of aluminum alloyat a time were adhesively joined with each other. On the following dayafter joining, the resulting test pieces were subjected to tensilebreaking tests, whereupon the average shear strength at break for thefour pairs was 43 MPa. This joining strength was lower than inExperiment example 13. Guessing on the basis of prior art, it wouldappear that, when a piece containing some amine-based compound stands ina wet state at an elevated temperature of more than 100° C., boehmiteformation occurs at the surface. The inventors, suspecting that boehmitecontaining hydroxyl groups is not always a substance having a toughhardness, thought the results to be reasonable.

Experiment Examination 17 Adhesion with A5052 Aluminum Alloy

As in Experiment example 13, pieces of A5052 sheet stock were degreasedand rinsed with water, subjected to preliminary pickling and rinsed withwater, etched with an aqueous solution of caustic soda and rinsed withwater, neutralized with an aqueous solution of nitric acid and rinsedwith water, then finely etched with an aqueous solution of hydrazinemonohydrate and rinsed with water. In addition, an aqueous solution ofhydrogen peroxide having a concentration of 5% was adjusted to 25° C.and the pieces were immersed therein for 5 minutes, then rinsed withwater. The aluminum alloy pieces were then dried by being placed in ahot-air dryer set to 67° C. for 15 minutes. Next, as in Experimentexample 1, two of the aluminum alloy pieces were adhesively joined witheach other at a time using the amine-curable epoxy adhesive EP-106(available from Cemedine, Japan). On the following day after joining,the resulting test pieces were subjected to tensile breaking tests,whereupon the average shear strength at break for the four pairs was 62MPa, which was very high.

Experiment Example 18 A7075 Aluminum Alloy

Commercially available A7075 sheet stock having a thickness of 3 mm wasacquired and cut to form a plurality of rectangular pieces measuring50×12 mm. Water was made ready in a tank and the commercially availablealuminum alloy degreaser NE-6 was added to the water to form an aqueoussolution of 60° C. having a concentration of 7.5%. The pieces ofaluminum alloy were immersed in the solution for 5 minutes, thenthoroughly rinsed with water. An aqueous solution of hydrochloric acidhaving a concentration of 1% and adjusted to 40° C. was made ready inanother tank and the aluminum alloy pieces were immersed therein for 1minute, then thoroughly rinsed with water. Next, an aqueous solution ofcaustic soda having a concentration of 1.5% was made ready in stillanother tank and the same aluminum alloy pieces were immersed thereinfor 4 minutes, then thoroughly rinsed with water. The aluminum alloypieces were then dried by being placed in a hot-air dryer set at 67° C.for 15 minutes. After drying, the aluminum alloy pieces were collectedtogether and wrapped with aluminum foil, then placed in a plastic bag,which was closed and stored.

Four days later, one of the pieces was examined with an electronmicroscope. The micrograph obtained is shown in FIG. 5. A strange, driedseaweed-like surface having diameter of 100 to 150 nm is apparent. Thiswas subjected to XPS analysis, whereupon large peaks for oxygen andaluminum and small peaks for magnesium, copper, zinc and sodium werenoted. In this case, surface treatment was completed with treatmentusing an aqueous solution of caustic soda and it was apparent thatrinsing with water was not sufficient to completely remove the sodiumions.

Experiment Example 19 A7075 Aluminum Alloy

Commercially available A7075 sheet stock having a thickness of 3 mm wasacquired and cut to form a plurality of rectangular pieces measuring50×12 mm. Water was made ready in a tank and the commercially availablealuminum alloy degreaser NE-6 was added to the water to form an aqueoussolution of 60° C. having a concentration of 7.5%. The pieces ofaluminum alloy were immersed in the solution for 5 minutes, thenthoroughly rinsed with water. An aqueous solution of hydrochloric acidhaving a concentration of 1% and adjusted to 40° C. was made ready inanother tank and the aluminum alloy pieces were immersed therein for 1minute, then thoroughly rinsed with water. Next, an aqueous solution ofcaustic soda having a concentration of 1.5% was made ready in stillanother tank and the same aluminum alloy pieces were immersed thereinfor 4 minutes, then thoroughly rinsed with water. Next, an aqueoussolution of nitric acid having a concentration of 3% and adjusted to 40°C. was made ready in another tank and the aluminum alloy pieces wereimmersed therein for one minute, then rinsed with water. Compared withExperiment example 18, this was an experiment example in which the stepof immersion in an aqueous solution of nitric acid was added to thesteps in Experiment example 18.

Next, the aluminum alloy pieces were dried by being placed in a hot airdryer set at 67° C. for 15 minutes. After drying, the aluminum alloypieces were collected together, wrapped with aluminum foil and thenplaced in a plastic bag, which was closed and stored. Four days later,one of the pieces was examined with an electron microscope. Themicrograph obtained is shown in FIG. 6. Compared with FIG. 5, thedifference was dramatic. While the periodicity of the depressions andprotrusions remained the same, the protuberant features in the driedseaweed-like pattern had all disappeared, resulting in a shape in whichonly low protrusions remained. The surface had clearly become smoother,even when seen at a microscopic level. Such a surface showed littlepromise of a high joining strength with adhesive.

Experiment Example 20 A7075 Aluminum Alloy

Commercially available A7075 sheet stock having a thickness of 3 mm wasacquired and cut to form a plurality of rectangular pieces measuring50×12 mm. Water was made ready in a tank and the commercially availablealuminum alloy degreaser NE-6 was added to the water to form an aqueoussolution of 60° C. having a concentration of 7.5%. The rectangularpieces of aluminum alloy were immersed in the solution for 5 minutes,then thoroughly rinsed with water. Next, an aqueous solution ofhydrochloric acid having a concentration of 1% and adjusted to 40° C.was made ready in another tank and the aluminum alloy pieces wereimmersed therein for 1 minute, then thoroughly rinsed with water.

Next, an aqueous solution of caustic soda having a concentration of 1.5%was made ready in still another tank and the aluminum alloy pieces wereimmersed therein for 4 minutes, then thoroughly rinsed with water. Anaqueous solution of nitric acid having a concentration of 3% andadjusted to 40° C. was made ready in another tank and the aluminum alloypieces were immersed therein for one minute, then rinsed with water.Next, an aqueous solution containing hydrazine monohydrate by 3.5% andadjusted to 60° C. was made ready in yet another tank and the aluminumalloy pieces were immersed therein for 2 minutes, following which theywere thoroughly rinsed with water, then dried by being placed for 15minutes in a hot air dryer set to 67° C. Compared with Experimentexample 19, this was an experiment in which the step of immersion in anaqueous solution of hydrazine hydrate was added to the steps inExperiment example 19. After drying, the aluminum alloy pieces werecollected together, wrapped with aluminum foil and then placed in aplastic bag, which was closed and stored.

Four days later, one of the pieces was examined with an electronmicroscope. The micrograph obtained is shown in FIG. 7. As is apparentwhen compared with FIG. 6, a strange pattern that resembles jumbledpiles of stones or boulders of 20 to 110 nm in diameter can be seen.Judging from FIG. 7 (with magnification of 10,000 times), the surfaceappears to be covered by depressions having diameters of between 40 and100 nm, with the number-average diameter being 60 nm. In an XPSexamination of another of the pieces, peaks for zero-valent aluminumsuch as those in Experiment example 1 were not observed.

The same day, the aluminum alloy pieces were taken out and lightlycoated on the respective ends with the commercially available epoxyadhesive EP-106. The pieces were placed in a desiccator with the coatedside facing upward, then the desiccator was evacuated with a vacuum pumpto 1 mmHg and left in this state for one minute, following which air wasintroduced, returning the interior to standard pressure. This operationof reducing the pressure and then returning to standard pressure wasrepeated three times, following which the pieces were removed from thedesiccator. These aluminum alloy pieces were transferred to the interiorof a hot air dryer and assembled into pairs by stacking two pieces withthe adhesive-coated sides placed against one another at a time so thateach joined face had an area of about 0.5 cm², a 500 g weight was placedat each joined face, the door was closed and the temperature was rapidlyraised to 135° C.

Forty minutes later, the hot air dryer setting was changed to 165° C.and the rise in temperature was awaited. Once the temperature hadreached 165° C., this state was held for 20 minutes, then the power onthe hot air dryer was turned off, the door of the dryer was opened andthe interior was allowed to be cooled. In tensile breaking testsconducted two days later on the resulting test pieces, the average shearstrength at break for the four pairs was 65 MPa, which was very high.

Experiment Example 21 Adhesion with A7075 Aluminum Alloy

In a similar way as in Experiment example 20, pieces of A7075 sheetstock were degreased and rinsed with water, subjected to preliminarypickling and rinsed with water, etched with an aqueous solution ofcaustic soda and rinsed with water, neutralized with an aqueous solutionof nitric acid, cleaned with water and supersonic vibration, againimmersed in an aqueous solution of nitric acid and rinsed with water,then finely etched with an aqueous solution of hydrazine monohydrate andrinsed with water. In addition, an aqueous solution of hydrogen peroxidehaving a concentration of 5% was adjusted to 25° C. and the aluminumalloy pieces were immersed therein for 5 minutes, then rinsed withwater. The pieces were subsequently dried by being placed for 15 minutesin a hot air dryer set to 67° C.

Four days later, one of the pieces was examined with an electronmicroscope. The results are shown in FIG. 8. The transition from FIGS. 7to 8 is due to the aqueous hydrogen peroxide, although how to describethe change in the images is not an easy matter. While there is not asubstantial difference in the periodicity of the fine depressions andprotrusions, FIG. 8 appears to show a well-defined shapes withoutunderlying features. One gets the sense that crystallization of thealuminum oxide has proceeded. Yet, when XRD analysis was carried out,peaks for aluminum oxide crystal were not observed. Observation with XRDis impossible without a certain amount of crystals; it is impossible todetermine whether the aluminum oxide was microcrystalline or was stillamorphous. Another piece was subjected to examination with a scanningprobe microscope and data on the roughness obtained. According to theresults, the mean peak spacing (RSm) was 3.5 μm and the maximum height(Rz) was 1.8 μm.

Next, in a similar way as in Experiment example 20, the aluminum alloypieces were adhesively joined together, two pieces at a time, using theepoxy adhesive EP-106. On the second day after joining, tensile breakingtests were carried out, whereupon the four pairs had an average shearstrength at break of 70 Mpa, which was very high.

Experiment Example 22 Adhesion with A7075 Aluminum Alloy

A plurality of square rod-shaped pieces measuring 3×4×18 mm were formedby cutting and mechanically working commercially available A7075 sheetstock having a thickness of 3 mm. Each of these pieces, with a hole of1.5 mm in diameter formed at an end thereof, was shaped so as tofacilitate liquid treatment, after which the pieces were used in thefollowing experiment. Specifically, liquid treatment was carried out inexactly the same way as in Experiment example 21. Next, an epoxyadhesive was applied on the end face on the side opposite to that wherethe hole was formed, the pieces were placed in a desiccator and pressurereduction/standard pressure recovery operations were carried out in thesame way as in Experiment example 21. Next, two pieces were buttedend-to-end, creating three pairs of joined objects having lengths ofabout 36 mm. Specifically, with the two pieces mutually abutting in eachpair, a tacky tape was wrapped around the vicinity of the junction tokeep the two pieces from separating and to keep the adhesive fromspilling out when the viscosity is lowered under elevated temperature.The three pairs wrapped about with tacky tapes were placed horizontallyon a plate inside a hot air dryer and weights were set on both ends tokeep them from extending, following which heating was carried out inexactly the same way as in Experiment example 21.

This experiment was carried out in order to measure the tensile strengthat break for pieces of A7075 stock which had been joined with an epoxyadhesive. Tensile break tests were carried out on the resulting joinedobject with the tensile testing machine, yielding an average value of 85kgf. Given the joining surface area of 0.12 cm², a tensile strength atbreak of 69 MPa was obtained. The average thickness of the adhesivelayer at this time was 0.25 mm. While there may be no specialsignificance, it was striking to note that the shear strength at breakand the tensile strength at break were substantially identical values,both being close to 70 MPa.

Experiment Example 23 Adhesive

A commercially available liquid single-pack dicyandiamide-curable epoxyadhesive EP-106 (available from Cemedine, Japan) was acquired.Separately, the ethylene-acrylic acid ester-maleic anhydride terpolymerBondine TX8030 (available from Arkema, France) was acquired,freeze-fractured at a liquid nitrogen temperature to obtain a powderthat passes through a 30 μm screen. In addition, glass fibers having anaverage fiber diameter of 9 μm and a fiber length of 3 mm (RES03-TP91,available from Nippon Sheet Glass, Japan) were acquired and lightlyground in a mortar. 100 g of the epoxy adhesive EP-106, 5 g of the abovepowdered polyolefin resin and 10 g of the above glass fibers were placedin a polyethylene beaker, thoroughly stirred and left to stand for onehour, after which the contents were again stirred to blend together theingredients. This mixture was used as the epoxy adhesive composition.

Aside from using the resulting adhesive composition in place of EP-106,this experiment was carried out in exactly the same way as Experimentexample 21. Two days after curing the adhesive, the test pieces weresubjected to tensile breaking tests, whereupon the average shearstrength at break for the four pairs was 69 MPa. Based on the resultsfrom Experiment examples 1 to 21, it is apparent that the joiningstrength is basically determined by the shape and physical properties ofthe metal surface. As the results in this experiment are substantiallythe same as those in Experiment example 20, this fact appears toindicate that the basic performance of the adhesive itself is unchangedbetween this experiment and EP-106. In fact, because the adhesive inthis experiment contains elastomer and the linear expansion coefficientought to be close to that of metal owing to the admixture of filler, itis expected from common knowledge in the art that good results should beachievable after experiencing vibrations or after experiencing elevatedtemperatures.

Experiment Example 24 Adhesive

The commercially available epoxy adhesive EP-106 was acquired. Inaddition, the glycidyl methacrylate-ethylene copolymer Bondfast E(available from Sumitomo Chemical, Japan), which is a polyolefin resin,was acquired and freeze-fractured at a liquid nitrogen temperature toobtain a powder that passes through a 30 μm sieve. 100 g of the epoxyadhesive EP-106, 5 g of the above powdered polyolefin resin and 10 g ofthe glass fibers RES03-TP91 were placed in a polyethylene beaker,thoroughly stirred and left to stand for one hour, after which thecontents were again stirred to blend together the ingredients. Thismixture was used as the epoxy adhesive composition. Aside from using theresulting adhesive composition in place of EP-106, this experiment wascarried out in exactly the same way as Experiment example 21. Two daysafter curing the adhesive, the test pieces were subjected to tensilebreaking tests, whereupon the average shear strength at break for thefour pairs was 70 MPa.

Experiment Example 25 Fabrication of Commercial-Type Prepreg

Ten parts by weight of a commercially available brominated bisphenolA-type solid epoxy resin (EPC-152, available from Dainippon Ink &Chemicals, Japan), 13.9 parts by weight of a bisphenol A-type liquidepoxy resin (EP-828, available from Yuka Shell Epoxy, JApan), 15 partsby weight of tetraglycidyl diaminodiphenylmethane (ELM-434, availablefrom Sumitomo Chemical, Japan), 24.8 parts by weight of a bisphenolF-type liquid epoxy resin (EPC-830, available from Dainippon Ink &Chemicals, Japan), 25 parts by weight of 4,4′-diaminodiphenylsulfone(4,4′-DDS, available from Sumitomo Chemical, Japan) as curing agents and0.3 part by weight of BF₃-monoethylamino complex (BF3-MEA), 8 parts byweight of a weakly crosslinked carboxyl-terminated solid acrylonitrilebutadiene rubber (DN-611, available from Nippon Zeon, Japan) and 3 partsby weight of the thermoplastic resin hydroxyl-terminated polyethersulfone (PES-100P, available from Mitsui Toatsu Chemicals, Japan)(thetotal amount of these ingredients being 100 parts by weight) were mixedat standard temperature and the mixture was formed into a sheet usingrollers.

The resulting resin films were set in a prepreg machine and were joinedunder applied pressure from both sides of carbon fibers (T-300,available from Toray, Japan) arranged in parallel in one direction asreinforcing fibers by a conventional method, thereby forming a prepreghaving a resin content adjusted to 38%. The fiber basis weight was 190g/m². Prepregs commercially available from various domestic corporationsappear to be manufactured by this type of method.

Experiment Example 26 Production and Evaluation of a Composite

A5052 aluminum alloy sheet stock having a thickness of 1.6 mm was cut toform a plurality of rectangular pieces measuring 45×15 mm. Liquidtreatment on these pieces was performed in the same way as in Experimentexample 18. That is, the pieces were, in order, degreased with anaqueous solution of the aluminum alloy degreaser NE-6 and rinsed withwater, subjected to preliminary pickling in a 1%-aqueous solution ofhydrochloric acid and rinsed with water, alkali etched in a 1.5%-aqueoussolution of caustic soda and rinsed with water, neutralized in a3%-aqueous solution of nitric acid and rinsed with water, finely etchedin an aqueous solution of hydrazine monohydrate and rinsed with water,oxidized in an aqueous solution of hydrogen peroxide and rinsed withwater and finally dried by being placed for 15 minutes in a hot airdryer set to 67° C.

After drying, the aluminum alloy pieces were collected together, wrappedin aluminum foil and stored. On the same day, the aluminum alloy pieceswere taken out and the liquid single-pack dicyandiamide-curable epoxyadhesive EP-106 (available from Cemedine, Japan) was lightly applied tothe ends. The pieces were then placed in a desiccator with theadhesive-coated sides facing upward, the pressure was reduced to 3 mmHgwith a vacuum pump and left in that state for 1 minute, following whichair was introduced, returning the desiccator to standard pressure. Thisoperation of reducing the pressure and then returning to standardpressure was repeated three times, following which the pieces wereremoved from the desiccator.

Meanwhile, the firing jig 1 shown in FIG. 1 was set up, a mold releasefilm 17 obtained by cutting 0.05 mm-polyethylene film into strips waslaid down within the metallic mold body 2 and the aluminum alloy sheet11 prepared above was placed thereon. A plain weave cloth of carbonfibers (T-300, available from Toray, Japan) that had been separately cutwas laid down as the prepreg 12 in FIG. 1. Three layers were built upthereon while applying to the consecutive layered surfaces an epoxyadhesive (EP-106) discharged from a syringe. Next, a mold releasepolyethylene film piece 13 was placed on the aluminum alloy sheet 11side, following which the size of the cloth was changed and five layerswere similarly built up while again applying adhesive.

The amount of EP-106 used was about 1 cc. PTEF blocks 14 and 15 wereplaced on top of the polyethylene film pieces 13 to hold everything downand then the entire assembly was placed in a hot air dryer. Within thedryer, a 0.5 kg iron weight was placed on top of each PTEF block 14 and15, following which the dryer was turned on and the temperature wasraised to 135° C. Heating at 135° C. was carried out for 40 minutes,after which the temperature was raised further to 165° C. over a periodof 5 minutes and the temperature was held at 165° C. for 20 minutes. Thepower was then turned off and the dryer was left to be in cooling statewith the door closed. The next day, the assembly was taken out of thedryer, the shaped object was released from the mold and the polyethylenefilm pieces 13 and 17 were peeled off, giving the aluminum alloycomposite 10 shown in FIG. 2. The same procedure was repeated to giveeight pieces of aluminum alloy composite 10 obtained by uniting aluminumalloy with CFRP.

On the second day after joining, four pieces were subjected to tensilebreak tests. The CFRP portion was sandwiched between two pieces of 1 mmthick SUS304 stainless steel polished with sandpaper and the resultingassembly was secured by clamping between chuck plates. The average shearstrength at break for the four pairs was 62 MPa, which was very strong.The joining surface area was calculated as l×m in FIG. 2.

Next, with regard to the remaining four pieces, the united objects wereclamped in a tensile testing machine in the same way as described aboveand subjected to a strain of 30 MPa, at which point the pullingoperation was stopped and the specimen was held in this state for 10minutes. The chuck was subsequently loosened and the specimen wasremoved from the testing machine and allowed to rest. The next day, whenthese specimens were subjected to a tensile breaking test, the averageshear strength at break was 60 MPa. There was thus no particular sign ofa decline in the joining strength.

Experiment Example 27 Production and Evaluation of a Composite

Using 45×15 mm rectangular pieces of A5052 aluminum alloy sheet stockhaving a thickness of 1.6 mm like those in Experiment example 26,similar test pieces for measuring adhesive strength were fabricated.That is, adhesive-coated aluminum alloy pieces were prepared by applyingan adhesive to the aluminum alloy, placing the adhesive-coated alloypieces in a desiccator and repeating three times the operation ofpressure reduction with a vacuum pump, followed by return to standardpressure. Next, the metallic mold 1, 2 and 3 shown in FIG. 1 was set up,a 0.05 mm thick polyethylene film cut into strips 4 was laid down in themold cavity and the aluminum alloy piece described above was placed ontop as 11. The procedure up to this point was the same as in Experimentexample 26, while the CFRP prepreg fabricated in Experiment example 25was used.

That is, three sheets of the prepreg in Experiment 25 that had been cutwere built up in layers, then polyethylene film 13 was placed on thealuminum alloy side, following which five sheets of prepreg of adifferent size were again built up in layers. A PTFE weight 9 was thenplaced on top and the assembly was placed in a hot air dryer. Within thedryer, a 0.5 kg iron weight was placed on top of each PTEF block 9,following which the dryer was turned on and the temperature was raisedto 135° C. Heating at 135° C. was carried out for 60 minutes, afterwhich the temperature was raised further to 165° C. over a period of 10minutes and the temperature was held at 165° C. for 60 minutes. Thepower was then turned off and the dryer was left to be in cooling statewith the door closed. The next day, the assembly was taken out of thedryer, the shaped object was released from the mold and the polyethylenefilm was peeled off, giving the shaped object shown in FIG. 2.

On the second day after joining, the objects were subjected to tensilebreaking tests. The CFRP portion was sandwiched between two pieces of 1mm thick SUS304 stainless steel polished with sandpaper and theresulting assembly was secured by clamping between chuck plates. Theaverage shear strength at break for the four pairs was 55 MPa, which wasvery strong. The joining surface area was calculated as l×m in FIG. 2.

What is claimed is:
 1. An aluminum alloy composite comprising: a firstmetal part made of a first aluminum alloy having a micron-order surfaceroughness formed by chemical etching on a surface thereof, the surfacehaving thereon a thin layer of aluminum oxide with a thickness of atleast 2 nm that is free of sodium ions and the surface roughness havingformed therein an ultrafine irregular surface formed of depressions orprojections having 10 to 100 nm diameter and substantially equal depthor height, and an adherent part joined to the first metal part with anepoxy-based adhesive that has penetrated into the ultrafine irregularsurface; wherein said micron-order surface roughness has a mean peakspacing: RSm of 0.8 to 10 μm and a maximum height: Rz of 0.2 to 5.0 μm;wherein said adherent part is fiber-reinforced plastic which containsthe epoxy-based adhesive and is filled, laminated and reinforced with atleast one selected from among continuous fibers, short fibers and fibercloth, wherein said epoxy-based adhesive in the cured form includes atotal of between 0 and 100 parts by weight of filler per 100 parts byweight of the total resin components, and wherein the shear strength atbreak with said first metal part and said second metal part is 44 to 60MPa.
 2. The aluminum alloy composite according to claim 1, wherein theshear strength at break with said first metal part and saidfiber-reinforced plastic as the adherent part is 50 to 60 MPa.
 3. Thealuminum alloy composite of claim 1, which is obtained by joining aplate part made of the aluminum alloy and a plate object of thefiber-reinforced plastic and has formed therein a throughhole forpassing a bolt or rivet therethrough.